Vat dyesttjffs of the anthraquinone



Patented Dec. 23, 1941 SERIES AND PROCESS OF THEM PREPARING Hans Schliohenmaier, LudwigrBerlin,and'WaIter Noll, Frankfort-on-the-Main, Germany, assignors to General Aniline & EilmGorporation, New

York, N. Y., a corporation of Delaware No Drawing. Application February 6, 19,41,8 1:-

rial No. 377,670. In Germany February-- 24,

6 Claims.

The present invention relates to vat dyestuffs of the anthraquinone series and to a process of preparing them.

We have found that new vat dyestuifs of the anthraquinone series may be obtained by heating to hightemperatures, for instance 230 C.-260 0., a compound of the general formula;

wherein X represents a member of the group consisting of hydrogen, chlorine, methyl and trifluoromethyl and Y represents a member ofthe group-consisting of hydrogen, chlorine and methyl. They are grey-blue to navy-blue vat dyestufis of, good fastness properties; They are distinguished above all by a. very good, fastness to spotting with water and yield tone-in-tone dyeings on mixed fabrics from cotton and. artir ficial silk. I I

The parent materials used for the preparatio of the vat dyestuffs may be obtained, for in-" stance, by reaction of corresponding -aminoacridones with alpha-chloronaphthalenes or corresponding 4-halogen-acridones" with alphanaphthylamines. The preparation of these parent materials and the carrying through of the present process may also be performed in one operation.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto; the parts are by weight:

(1) 22 parts of 4-amino-2.l-anthraquinone- 1'.2-benzacridone of the formula:

areslowly heated, whiletstirring; to 210 C'. to"- gether with 250' parts; of alpharchloronaphthalene, 15-parts of potassium carbonate and: lpart of, copper: acetate. The blueegreen; solution gradually ,turns green. The compound of the following formula is; obtained.

Bordeaux vat. In the usual organic solvents A such as benzene, chlorobenzene the dyestuff is nearly insoluble even in the heat; its solubility is better in nitrobenzene or trichlorobenzene at boiling temperature. The dyestufi yields bluegrey dyeings which are fast to spotting with water. On mixed fabrics of cotton and artificial silk tone-in-tone dyeings are obtained.

(2) 32.8 parts of 4-amino-2J-anthraquinone- 1".2' -benz-4 -trifiuoromethyl-acridone are heated "for'2 hours at 220 0. together with 500 parts of 'alpha-chloronaphthalene, 0.5 part of copper acetate and 5 parts of potassium carbonate. To the reaction mixture which contain the compound ofthe formula:

there are added parts of nitrobenzene and the whole is then heated to 240 C.-250 C. until a test portion taken from the mixture no longer yields' a violet vat but an olive-brown vat. The whole is then allowed to cool, filtered with suction and the'solid matter isdried ln'order to purify the dyestuffit'is either re-vatted with caustic soda solution and hydrosulfite or sublimed under a very reduced pressure. After crystallization from nitrobenzene fine blue needles are obtained melting at 420 C. The dyestufi dissolves in sulfuric acid to a blue-green solution. From'a'n olive-brown vat it dyes mixed fabrics from cotton and artificial silk staple fiber navy-blue shades. The dyeings are fast to spotting with water and uniform.

(3) 8.2 parts of 4-amino-2.1-anthraquinone- 2'.1'-benz-4'-trifiuoromethyl-acridone are heated to boiling together with 20 parts of 1.8-dichloronaphthalene in.l00 parts of nitrobenzene in the presence of 6 parts of potassium carbonate and 1 part of copper'acetate. The dyestuff dissolves The temperature is then raised to 240 C.-

first to a green solution with formation of the following compound:-

and then to a blue solution with formation of the final dyestufi which is identical with the compound obtained according to Example 2.

(4) 9.4 parts of 4-bromo-L2-anthraquinone- 1' .2-benz-4'-trifluoromethyl-acridone obtainable from 4-amino-1.2-anthraquinone-lf.2'.-benz-4'- trifluoromethylacridone by substituting bromine for the amino-group according to Sandmeyer, are heated for about 20 hours at 130 C. together with 20 parts of alpha-naphthylamine, 6 parts of potassium carbonate and 1 part of copper acetate. The whole is then allowed to cool, filtered with suction and the solid matter is recrystallized. Green crystals are thus obtained which melt at 358 C.-360 C. 20 parts of this compound having the formula:

are heated at 240 (#250? C. in parts of alpha-chloronaphthalene together with 10 parts of potassium carbonate and S'parts of nitrobenzene until a test portionyields no longer a violet but a brown-olivefvat If this is the case, the dyestufi obtained is purified as described in Example 2. It isidentical with that obtained according to Example 2.

(5) 25.8 parts of 4-amino-2.1-anthraquinone- 122'-benzene-4'-chloracridone are heated at about 250? C.260 C. for about 20 hoursin 250 parts .of;alpha chloronaphthalene in the presence of 10 parts of potassium carbonate and 05 part ofcopper acetate; The-dyestufl' is obtained from a primary compound which has the following formula:

After cooling, the whole is filtered with suction and the dyestuff is purified by re-vatting. Crystallized from trichlorobenzene it forms blue needles melting at 445 C. It, dissolves in concentrated sulfuric acid to a blue solution; it yields a brown-olive vat. The dyestufi dyes mixed fabrics from cotton and artificial silk staple fiber uniform navy-blue shades which are fast to spotting with water. Instead of copper acetate there may also be used a small quantity of copper powder (natural copper C) and instead of potassium carbonate there may likewise be used sodium carbonate.

Similarly to the 4-amino-2.1-anthraquinonel.2'-benz-4-chloracridone the 4-amino-2.1-anthraquinone-1.2'-benz-5'-chloracridone is melted with l-chloronaphthalene to the corresponding dyestufi. It melts at about 470 0., dissolves in concentrated sulfuric acid to a blue-green solution and dyes cotton and artificial silk from an olive vat after exposure to the air. grey shades which are fast to spotting with water.

(6) 27 parts of 4-amino-2.1-anthraquinone- 2'.1-benz-3.5-dichloracridone are heated to boiling for 30-4Q hours in 250 parts of alphachloronaphthalene together with parts of potassium carbonate and 0.5 part of copper acetate. From the components there is first obtained the compound of the following formula:

which then passes into the dyestuff. After revatting and crystallization from nitrobenzene blue needles are obtained which melt at 415 C. The dyestuif dissolves in concentrated sulfuric acid to a blue-green solution and dyes mixed fabrics from cotton and artificial silk staple fiber navy-blue tone-in-tone dyeings which are fast to spotting with water.

(7) 1.6 parts of 4;-amino-2.1eanthraguinone- 2.1'-benz-4'-trifluoromethylacridone are heated at 190 C. for about 5 hours in 150 parts of nitrobenzene together with 150 parts of 1.5-dichloronaphthalene, 0.5 part of copper acetate and 2.5 parts of potassium carbonate. The mixture thereby becomes green and a test portion taken therefrom after cooling and examined with the microscope shows uniform green crystals. The whole is allowed to cool and the compound formed is filtered with suction. 10 parts of this compound of the following formula:

CFa

are heated to boiling together with parts of =alpha-chloronaphthalene and 3 parts of potassium carbonate until atest portion taken therefrom yields a brown-olive vat. If this is the case, the cooled reaction product is filtered with suction. The dyestuff crystallizes from nitrobenzene in the form of blue small needles containing chlorine and melting at 420 C. It dyes mixed fabrics from cotton and artificial silk staple vfiber somewhat redder: shades than the dyestuif freefromchlorine. The dyeings are fast to spotting with water and, tone-.in-tone. A dyestuff which likewise cohtain'schlorine but, at a different position is. obtained by using 1.4-dichloronaphthalene instead of 1.5-dichloronaphthalene. It melts at 415 C.

We claim:

1. The products of the general formula:

wherein X represents a member of the group consisting of hydrogen, chlorine, methyl and trifluoromethyl and Y represents a member of the group consisting of hydrogen, chlorine and methyl, being blue vat-dyestuifs of good fastness properties.

2. The products of the general formula:

wherein Y represents a member of the group consisting of hydrogen, chlorine and methyl, being blue vat dyestuffs of good fastness properties.

3. The product of the formula:

HN/ @gioo o dyeing mixed fabrics from cotton and artificial silk staple fiber from an olive-brown vat uniform navy-blue tints fast to spotting with water.

4. The product of the formula:

forming blue needles, melting at 420 C. and

yielding on mixed fabrics from cotton and artificial silk staple fiber uniform tints which are fast to spotting with water and somewhat redder than the dyestufi free from chlorine.

5. The dyestuif of the formula:

HN o t Hi I I wherein X represents a member of the group consisting of hydrogen, chlorine, methyl and trifluoromethyl, and Y represents a member of the group consisting of hydrogen, chlorine and methyl and Z represents a member of the group consisting of hydrogen and chlorine, until the formation of the vat dyestuff is finished.

HANS SCI-ILICHENMAIER. LUDWIG BERLIN. WALTER NOLL. 

